Disazo-dyestuffs



2,769,806 Patented Nov. 5, 1956 United States Patent ice at low temperatures, that is to say, below C., that coupling with 2-arylarnino-5 hydroxynaphthalene-7-sulfonic acid can be carried out successfully without the aid of unusual precautionary measures. However, it is generally advisable either not toallow the tetrazotiza-tion mixture to become too strongly acid or to avoid a large excess of mineral acid. For this reason it is of advantage to carry out the tetrazotiza-tion with an alkali nitrite with the addition of a carboxylic acid such, for example, as acetic acid 0 or benzoic acid. It is of course of advantage to use the diazo compound as soon as possible after its production.

The disulfuxie acid esters are coupled with Z-arylamiho- S-hydroxynaphth'alene-7 sulfonic acids which may contain in the aryl radical further substituents, and advantageously This invention provides new disazo-dyes'tutfs' which, those which do-not impart solubility. As examples there like, for example, the dyestuli of the formula may be mentioned 2-"(i' methylphenylamino) 2 -(4- (1) OH N&OO;;SO (R-SOr-ONa HO correspond to the general formula methylphenylamino)-, 2 (4' methoxyphenylamino)-,

OH XOO2S? 0-SOr-OX HO I I l Aryl-HN 0 K XOSS in which each X represents a cation.

These dyestufisare made in accordance with the inven- V tion by treating 3:3 dihydroxy-4:4 -diaminodiphenyl, on The coupling of tetrazotized 3:3"-dihydroxy-4:4-dithe one hand, to convert the two hydroxyl groups in. the aminodiphenyl disulfuric acid ester with the 2-arylamino- 3'- and 3'-posi'ti ons of the diphenyl: radical into acid sul- 3.5 S-hydroxynaplithalene 'l-sulfonic acids may be carriedout furic acid ester groups and, on the other, to diazotize the by the usual known methods, advantageously in an alkatwo amino groups inthe 4- and 4-positi ons1 of the. diline medium, for example, a medium rendered alkaline phenylradical and couple them with a Z-arylamino-S-hywith an alkali carbonate, an alkali hydroxide or an alkadroxynaphthalene-7-sulfonic acid, and carrying out the line earth metal hydroxide,- and if desired, with the use aforesaid treatments in either order of succession. 40 of stable additions such as alcohols, acetone, pyridine,

Thus, the. dyestuffs. of the formula. (2) can be made picolin'es or' ethanolaniine's. either by coupling. tetrazotized 3:3 dihydroxy-4:4' dia- In making the dyestuffs in accordance with the second minodiphenyl disulfuric acid ester onboth sideswitha 2 form of the process referred to above the tetrazotized arylamino-S-hydroxynaphthalene-7 sulfonic acid or by 3:3-dihydroxy-4:4'-diaminodiphenyl is first coupled on converting into sulfuric acid ester groups the hydroxyl' both sides with a 2-arylamino-5-hydroxynaphthalene-7- groups in the 3- and 3"-positions of'the. diphenylradical sulfonic acid, advantageously one of the azo components ofadisazo-dyestufi obtained'by coupling tet'razotized323-'- of this kind mentioned above, and then the hydroxyl dihydroxy-4:4-diamino-diphenyl onboth sideswith a groups inathe 3- and- 3-'-positions of the diphenyl radical 2 arylamino-5'-hydroxynaphthalene-7-sulfonic acid. are converted into sulfuric acid ester groups. The cou- The disulfuric acid esters used in the form of the proc- 0 pling is advantageously carried out in a strongly alkaline ess first mentioned in the precedingparagraph can be medium, for example,.amedium rendered alkaline with an made by reacting 3:3'-dihydroxy-4:4'-diamino-diphenyl with chloro-sulfonic acid in an inert organic dispersing, medium. As dispersingmedia there may be mentioned, for example, dioxane or halogenated hydrocarbons such as chlorobenzenes,. carbon tetrachloride; chloroform: or tetrachlorethane. Only a small: excessof chlorosulfonic acid is required, for example, an excess of IO ZO' percenttpyridine base suchas pyridine itself or a picoline at a The reaction-takes place with agentle evolution of heat, moderately raised temperature. The dyestui'l is advanand a reaction temperature slightly aboveroomtemperatageously recovered from the reaction mixture by disture, for example,.about 40 C. to 60 C.,-is advantageous tilling off the base in vacuo and neutralizing the radical As the sulfuricacid esters so:obtained are only slightly with an alkali carbonate; soluble in most dispersing, media they can easilybe sep-' The dyestuffs obtained by the present process possess a arated from the reaction mixture by filtration. For the good solubility in waterin=the form of their alkali salts, subsequent tetrazotization itis of advantage to convert and can be used for dyeing or printinga very wide variety the sulfuric acid ester into an alkali. salt, for example, ofmaterials, for example'those of animal origin, such as by reaction with analkali carbonate, especially sodium leather, wool or silk, but especially cellulose-containing carbonate, in the cold. If desired the sulfuric acid ester materials such as linen, cotton, or artificial silk or staple or its alkali saltmay be dried. fibers of regenerated cellulose, and also artificial fibers of The. tetrazotization of'the disulfuric acid ester is adsuperpolyamides or super-polyurethanes. vantageously carried out at a low temperature. It is sur- The dyestufis can be'converted by known methods into prising, that the diazo compound so obtained is so stable complex metal-compounds, for example, the complex DISAZO-DYESTUFFS Oscar Weber, Reinach, Switzerland, assignor to Ciba Limited, Basel, Switzerland, a Swiss firm NoDrawing. Application April 6, 1953,

Serial No. 347,147 Claims priority, application Switzerland April 10, 1-952 6" Claims. (Cl. 260-182) NHO 2- 4'-chloroph'enyl'a m ino and 2-phenylamin0-S-hydroxynaphthalene-T-sulfonic; acid;

capable of assistingv coupling may also be used such as pyridine, picolines, alcohol, acetone or ethanolamine.

The esterification of the two hydroxyl groups in the diphenyl radical of the dyestuffs soobtained is advantageously conducted in a tertiary base, for example, a

alkali. or alkaline earth metal hydroxide, and additionsiron, manganese, chromium, cobalt, nickel or copper compounds of the corresponding ortho:ortho-dihydroxyazo-dyestuffs. Conversion into the metal complexes may be carried out in known manner in substance or on the azo-metal complexes on the fiber accompanied by the splitting off of the sulfuric acid ester groups takes place very easily, and there are obtained dyeings or prints which are distinguished by their good properties of fastness and fiber or partially or wholly in the dyebath. 5 the purity of their tints.

When the metal-free dyestuffs are used for dyeing cel- The following examples illustrate the invention, the lulose-containing fibers, the dyestuffs are advantageously parts and percentages being by weight: converted on the fiber, for example by known methods Example 1 into the complex cobalt, nickel or advantageously copper compounds of the ortho:ortho-dihydroxy-azo-dyestuffs. Parts of 3I3"dil1YdfXY-4?4'-diami110diPheI1Y1 are The dyeings may, for xa le, b t t d with copper stirred well in 50 parts of chloroform. 14.2 parts of sulfate in a fresh bath, It is also f advantage to use th chlorosulfonic acid are introduced dropwise into the reprocess of U. s. Patent No. 2,148,659, filed April 2, 1936 sulting suspension i the course of 2 minutes a room by Fritz Straub and Walter Anderau in which there are temperature- After Stirring the mixture one hour at carried out in the same bath fir t dyeing d th the 50-60 C. it is filtered. The filter paste is then converted treatment with the agent yielding metal. As an agent into the disodium salt by introducing it into a mixture of yielding metal for this purpose there is advantageously 60 Parts Of anhydrous Sodium Carbonate, 50 Parts of used an agent yielding copper, and especially one which is water and 50 parts of ice. The disodium salt is filtered stable towards alkaline solutions, such as a complex copff With suction, and when dry it is a stable preparation. per tartrate or sodium copper pyrophosphate. The disodium salt of the disulfuric acid ester is an al- Very val able dyeings are also obtained by using the most colorless powder which dissolves in water without process in which a dyeing or printing produced with the leaving y esiduemetal-free dyestufi is after-treated with an aqueous solu- T Paste tain a8 d ri d ve is intimately tion which contains a basic formaldehyde condensation mixed With 75 parts of ice, 80 parts of a saturated soluproduct of a compound which contains at least on e th tion of sodium chloride and 6.9 parts of sodium nitrite. atomic grouping 32 parts of acetic acid of 85 percent strength are then poured in. The mixture is stirred for a short time at a /N\ temperature below 0 C. until the nitrous acid has disappeared.

N 0\ 31.5 parts of 2-phenylamino-S-hydroxynaphthalene-7- sulfonic acid are dissolved in 150 parts of water and 20 or a compound such as cyanamide which is easily con- Parts of sOqh-lm hydroxide sohition of 30 percent strength vertible into a compound containing the aforesaid groupzfi r isggg g g g sg ggg g gg zi gj 532:5:

35 6O to 615969 P the above described tetrazo-solution is added all at o nce. Cellulose-containing materials can be dyed with great t zg i i sg i ggg ig fi ggi g g gj g zg igig adyantage by the dlsazp'dyesmfis of mventlon by suction, and the paste so obtained is suspended in 500 i a l i ig ugdanialme dslebathdwhlch has 13661] f 40 parts of water. Sodium carbonate is added until the regggi 3 ag L sg zg gls ggi gggl g i g s g action is alkaline, and the product is salted out and filtered off. The dyestuif so obtained is a dark powder WhlCh i i from the a g g two cal-boll: f a dissolves in water, sodium carbonate and dilute sodium 333;; s gg g gg: ggzfi f' g one acld hydroxide solution with a blue coloration and in concen- 4 trated sulfuric acid with -a blue green coloration. It cor- Hm+2Pm03m+1 responds to the formula OH NaO SO (|)SO Na HO ONE 40in nots- NH in which in represents a whole number, for example 2, and dyes cotton by the single bath or Z-bath aftercopperan alkali-resistant compound of a metal having an atomic number from 27-29, advantageously a compound of this kind in which the metal forms the constituent of the aforesaid phosphorus compound, and a dyestuft' of the formula (2). As agents yielding metal of the above kind there may be used advantageously an alkali copper pyrophosphate, and as the added amine 1:2-di-(fi-hydroxyethylamino)-ethane is especially useful.

In carrying out the dyeing process described above there are used with advantage stable dyestutf preparations, which are characterized in that they contain an alkali copper pyrophosphate or polyphosphate and the dyestuff. In preparing the dyebath or a stock solution to be used for preparing the dyebath, it is only necessary to dissolve in water an amine of the kind described above, in addition to the preparation just described. In the case of solutions of high concentration, such as stock solutions, it is of advantage to avoid the addition of electrolytes such as sodium chloride or sodium sulfate.

In the methods of printing and dyeing hereinbefore described the formation of the ortho:ortho'-dihydroxying process greenish blue tints having very good properties of wet fastness.

Example 2 65 parts of chlorosulfonic acid are added dropwise to 600 parts of pyridine, while the temperature is maintained at 20-30" C. by external cooling. There are then added in the course of 30 minutes 86.8 parts of the disazo-dyestuff obtained by coupling tetrazotized 3:3'-dihydroxy- 4:4 diaminodiphenyl with 2 phenylamino-5-hydroxynaphthalene-7-sulfonic acid, and the mixture is stirred for 5-6 hours at 60-65 C. The pyridine is distilled off in vacuo, and the oily residue is neutralized with sodium carbonate solution of 10 percent strength. The precipitated dyestulf is filtered off and dried. It has the same properties as the disazo-dyestutf obtained as described in Example 1.

By esterifying in the manner described above the disazo-dyestutfs from 1 mol of tetrazotized 3:3-dihydroxy-4:4'-diaminodiphenyl and 2 mols of 2-(2'- methyl-phenyl-amino)-or of 2-(4-methylphenylamino)- 2,.789,8G6 :1 6 or of 2-(4-chloro-phenylamino)- or of 2-(4'-methoxydried. There is obtained a blue dyeing-.011- good fastness phenylamino) 5 hydroxynaphthalene 7 sulfonic acid, to light and very good fastness to washing.

there are obtained products having similar properties and (b) 1.5 parts of complex sodium copper tartrate of corresponding to the formulae approximately neutral reaction are added to the dyebath OH Naoiso osoiNa H N=N N=N Q-HN soiNe mots NH CH: Hai

(|)H NaO S(I) 0SO=Na H0 N=N A N=N HsOG-HN soiNa Naoas amQ-cn.

OHT Naoisq OSOaNa HO N=N N: OIOHN -so.Na more f-N-H-O-Cl respectively Example 3 cooled to about 70 C., coppering is canried on for /2 100 parts of cotton are entered at into a hour at about 80 C. and the dyeing 1s rinsed with cold bath consisting of 4000 parts of Water, 2 parts of 35 water. If desired, the dyeing 1s soaped by after-treatment anhydrous sodium carbonate and 0.3 part of the dyestuff f 1/2 hour In a bath Whlch contams grams of obtained as described in the first, second and third paraselne? p and 2 grams fi y f SOdlllm Carbonate graphs of Example 1, Q in the first paragraph of Example per liter of Water. There is obtalned a blue dyeing of 2. The temperature is raised to 90-95" C. in the course good fastness to light and very good fastness to washing. of minutes, parts of crystalline sodium sulfate are I claim: added, and dyeing is carried on for 30 minutes at 90-100" 1. A disazo-dyestuff which in its firee acid form cor- C. The bath is then allowed to cool to about 70 C. and responds to the formula (3H HOO;S(|) (|)SO;OH

R-HN -SO3H H035 NH-R the further treatment is as described below under (a) or in which each R represents a radical of the benzene series (b). free from groups imparting solubility.

(a) The dyeing is rinsed with cold water and treated 2. A disazo-dyestufi which in its free acid form corfor /2 hour at -70 C. in a bath which contains 4000 responds to the formula 0H H00is- 0 0-so20H HO 3. A disazo-dyestufi which in its free acid form corparts of water, 3 parts of crystalline copper sulfate and 60 responds to the formula Q-HN -S05H noas 411146 I on.

4. A disazo-dyestufi which in its free acid form cor- 3 parts of acetic acid. The material is then rinsed and responds to the formula l I l moOHN SO;H Ems -NHG0H,

5. A disazo-dyestufi which in its free acid form corresponds to the formula 6. A disazo-dyestufi which in its free acid form corresponds to the formula References Cited in the file of this patent UNITED STATES PATENTS 

2. A DISAZO-DYESTUFF WHICH IN ITS FREE ACID FORM CORRESPONDS TO THE FORMULA 